EP1374918A1 - Ethylene oxide sterilization indicator inks - Google Patents
Ethylene oxide sterilization indicator inks Download PDFInfo
- Publication number
- EP1374918A1 EP1374918A1 EP03010105A EP03010105A EP1374918A1 EP 1374918 A1 EP1374918 A1 EP 1374918A1 EP 03010105 A EP03010105 A EP 03010105A EP 03010105 A EP03010105 A EP 03010105A EP 1374918 A1 EP1374918 A1 EP 1374918A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- water
- based chemical
- chemical indicator
- ethylene oxide
- ink
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 title claims abstract description 78
- 230000001954 sterilising effect Effects 0.000 title claims abstract description 53
- 238000004659 sterilization and disinfection Methods 0.000 title claims abstract description 51
- 239000000976 ink Substances 0.000 title abstract description 47
- 239000000126 substance Substances 0.000 claims abstract description 76
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 71
- 238000000034 method Methods 0.000 claims abstract description 57
- 239000007793 ph indicator Substances 0.000 claims abstract description 52
- 230000008859 change Effects 0.000 claims abstract description 38
- 230000008569 process Effects 0.000 claims abstract description 21
- FRPHFZCDPYBUAU-UHFFFAOYSA-N Bromocresolgreen Chemical compound CC1=C(Br)C(O)=C(Br)C=C1C1(C=2C(=C(Br)C(O)=C(Br)C=2)C)C2=CC=CC=C2S(=O)(=O)O1 FRPHFZCDPYBUAU-UHFFFAOYSA-N 0.000 claims abstract description 11
- UDSAIICHUKSCKT-UHFFFAOYSA-N bromophenol blue Chemical compound C1=C(Br)C(O)=C(Br)C=C1C1(C=2C=C(Br)C(O)=C(Br)C=2)C2=CC=CC=C2S(=O)(=O)O1 UDSAIICHUKSCKT-UHFFFAOYSA-N 0.000 claims abstract description 9
- 230000002427 irreversible effect Effects 0.000 claims abstract description 9
- CEQFOVLGLXCDCX-WUKNDPDISA-N methyl red Chemical compound C1=CC(N(C)C)=CC=C1\N=N\C1=CC=CC=C1C(O)=O CEQFOVLGLXCDCX-WUKNDPDISA-N 0.000 claims abstract description 9
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 21
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 11
- 150000007513 acids Chemical class 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 10
- YZORUOZKRBVLEG-UHFFFAOYSA-M sodium;4-[[4-(diethylamino)phenyl]diazenyl]benzenesulfonate Chemical compound [Na+].C1=CC(N(CC)CC)=CC=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 YZORUOZKRBVLEG-UHFFFAOYSA-M 0.000 claims description 10
- 239000000758 substrate Substances 0.000 claims description 10
- -1 aluminum silicates Chemical class 0.000 claims description 9
- 239000002562 thickening agent Substances 0.000 claims description 9
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical group O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000006260 foam Substances 0.000 claims description 7
- 239000012463 white pigment Substances 0.000 claims description 7
- 239000011230 binding agent Substances 0.000 claims description 6
- 230000000694 effects Effects 0.000 claims description 6
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 5
- 150000004687 hexahydrates Chemical class 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 229920000609 methyl cellulose Polymers 0.000 claims description 5
- 239000001923 methylcellulose Substances 0.000 claims description 5
- 235000010981 methylcellulose Nutrition 0.000 claims description 5
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- 229920005862 polyol Polymers 0.000 claims description 4
- 239000004408 titanium dioxide Substances 0.000 claims description 4
- 239000000391 magnesium silicate Substances 0.000 claims description 3
- 235000012243 magnesium silicates Nutrition 0.000 claims description 3
- OORQUAGUOJMPCS-UHFFFAOYSA-N 4-[[4-(diethylamino)phenyl]diazenyl]benzenesulfonic acid Chemical compound C1=CC(N(CC)CC)=CC=C1N=NC1=CC=C(S(O)(=O)=O)C=C1 OORQUAGUOJMPCS-UHFFFAOYSA-N 0.000 abstract 1
- 239000000975 dye Substances 0.000 description 30
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 9
- 239000007789 gas Substances 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000011449 brick Substances 0.000 description 4
- 239000004615 ingredient Substances 0.000 description 4
- 229910001629 magnesium chloride Inorganic materials 0.000 description 4
- 244000005700 microbiome Species 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- GNTPCYMJCJNRQB-UHFFFAOYSA-M sodium;2-[[4-(dimethylamino)phenyl]diazenyl]benzoate Chemical compound [Na+].C1=CC(N(C)C)=CC=C1N=NC1=CC=CC=C1C([O-])=O GNTPCYMJCJNRQB-UHFFFAOYSA-M 0.000 description 3
- VADKRMSMGWJZCF-UHFFFAOYSA-N 2-bromophenol Chemical compound OC1=CC=CC=C1Br VADKRMSMGWJZCF-UHFFFAOYSA-N 0.000 description 2
- GZFGOTFRPZRKDS-UHFFFAOYSA-N 4-bromophenol Chemical compound OC1=CC=C(Br)C=C1 GZFGOTFRPZRKDS-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000002168 alkylating agent Substances 0.000 description 2
- 229940100198 alkylating agent Drugs 0.000 description 2
- 239000000347 magnesium hydroxide Substances 0.000 description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000004338 Dichlorodifluoromethane Substances 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 238000005273 aeration Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000002421 anti-septic effect Effects 0.000 description 1
- 229940064004 antiseptic throat preparations Drugs 0.000 description 1
- 239000003443 antiviral agent Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000000090 biomarker Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- WBLIXGSTEMXDSM-UHFFFAOYSA-N chloromethane Chemical compound Cl[CH2] WBLIXGSTEMXDSM-UHFFFAOYSA-N 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 239000013530 defoamer Substances 0.000 description 1
- PXBRQCKWGAHEHS-UHFFFAOYSA-N dichlorodifluoromethane Chemical compound FC(F)(Cl)Cl PXBRQCKWGAHEHS-UHFFFAOYSA-N 0.000 description 1
- 235000019404 dichlorodifluoromethane Nutrition 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000008029 eradication Effects 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 230000002070 germicidal effect Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 208000015181 infectious disease Diseases 0.000 description 1
- 231100000518 lethal Toxicity 0.000 description 1
- 230000001665 lethal effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- DHRRIBDTHFBPNG-UHFFFAOYSA-L magnesium dichloride hexahydrate Chemical compound O.O.O.O.O.O.[Mg+2].[Cl-].[Cl-] DHRRIBDTHFBPNG-UHFFFAOYSA-L 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000012569 microbial contaminant Substances 0.000 description 1
- 230000002906 microbiologic effect Effects 0.000 description 1
- 230000009972 noncorrosive effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000011664 signaling Effects 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- MZSDGDXXBZSFTG-UHFFFAOYSA-M sodium;benzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=CC=C1 MZSDGDXXBZSFTG-UHFFFAOYSA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000003330 sporicidal effect Effects 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 239000012815 thermoplastic material Substances 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 239000012855 volatile organic compound Substances 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2/00—Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor
- A61L2/16—Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor using chemical substances
- A61L2/20—Gaseous substances, e.g. vapours
- A61L2/206—Ethylene oxide
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2/00—Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor
- A61L2/26—Accessories or devices or components used for biocidal treatment
- A61L2/28—Devices for testing the effectiveness or completeness of sterilisation, e.g. indicators which change colour
Definitions
- the present invention relates to ethylene oxide sterilization process indicators and, more particularly, to chemical indicator inks that are designed to undergo an irreversible color change when exposed to ethylene oxide vapor in the presence of low-temperature steam, and to methods for indicating that an article has undergone ethylene oxide sterilization processing.
- compositions such as germicides, antiseptics and bacteriostats are effective in controlling widespread growth of biological contaminants, they do not go as far as to completely eliminate these agents.
- ethylene oxide gas generally in an admixture with an inert gaseous diluant such as carbon dioxide, nitrogen, tricloromonofluoromethane, dichlorodifluoromethane, and the like.
- Ethylene oxide gas can be used as a sporicidal and virucidal agent. Consequently, ethylene oxide sterilization processes are often employed to ensure total eradication of microorganisms.
- ethylene oxide gas readily diffuses through all of the commonly employed packaging materials and is highly effective in killing microorganisms at temperatures well below those required for heat sterilization techniques, it enables efficient sterilization of many items, particularly those made of thermoplastic materials, which cannot withstand heat sterilization.
- the process generally involves placing an item in a chamber and subjecting it to ethylene oxide vapor. When used properly, ethylene oxide is not only lethal to all known microorganisms at ordinary temperature, but it is also non-corrosive, readily removed by aeration, easily handled and stored, and has a low toxicity to humans.
- the present invention meets this need by providing water-based chemical indicator inks that contain at least one pH indicator dye.
- the inks are effective in showing whether or not treated materials have been subjected to sterilizing conditions using ethylene oxide as the sterilization medium.
- a water-based chemical indicator ink for ethylene oxide sterilization processes containing at least one pH indicator dye selected from the group consisting of Bromocresol green, Bromophenol blue, Methyl red, Ethyl orange, and combinations thereof.
- the pH indicator dye undergoes an irreversible color change when exposed to ethylene oxide vapor in the presence of low-temperature steam.
- the low-temperature steam has a temperature of less than about 145°F.
- the pH indicator dye when exposed to other sterilization processes such as formaldehyde gas, high-temperature steam, dry heat, or combinations thereof, either does not undergo a color change or undergoes a color change that is different than is obtained when exposed to ethylene oxide vapor.
- the water-based chemical indicator ink can comprise a solution including the pH indicator dye dissolved in water.
- the water-based chemical indicator ink can further contain a powdered and crystallized hexahydrate metal salt.
- the water-based chemical indicator ink can further contain an acidic compound such as citric acid, at least one thickening agent, a white pigment such as titanium dioxide, a binder, and/or a foam suppressor such as an aliphatic polyol blend.
- the acidic compound retards a color change of the water-based chemical indicator ink.
- the thickening agent can be selected from the group consisting of hydrous aluminum silicates, hydrous magnesium silicates, and combinations thereof.
- the binder can be a polymeric material selected from the group consisting of polyvinyl alcohol, methyl cellulose, and combinations thereof.
- a method for indicating that an article has undergone ethylene oxide sterilization processing.
- the method comprises providing a water-based chemical indicator ink containing at least one pH indicator dye selected from the group consisting of Bromocresol green, Bromophenol blue, Methyl red, Ethyl orange, and combinations thereof.
- the pH indicator dye undergoes an irreversible color change when exposed to ethylene oxide vapor in the presence of low-temperature steam.
- the method further comprises applying the water-based chemical indicator ink to an article, subjecting the article to a concentration of ethylene oxide vapor in the presence of low-temperature steam, and observing the chemical indicator ink for a color change that is visually indicative of whether the concentration of ethylene oxide vapor has been applied for a time sufficient to sterilize the article.
- the method can further comprise measuring the integrated effect of subjecting the article to the concentration of ethylene oxide vapor in the presence of low-temperature steam for the time sufficient to sterilize the article.
- the method can comprise applying the water-based chemical indicator ink to a substrate to form an ethylene oxide sterilization process indicator prior to applying the ink to the article.
- the step of applying the water-based chemical indicator ink to a substrate can be accomplished by printing the ink on the substrate in the shape of squares or insignia to form the indicator.
- the indicator can be secured to a package containing the article and subjected to the concentration of ethylene oxide vapor in the presence of low-temperature steam.
- a feature of the present invention to provide a water-based chemical indicator ink for printing insignia on a substrate that is visually indicative of whether a concentration of ethylene oxide has been applied for a time sufficient to ensure sterilization within a treating chamber or within the contents of a package subjected to ethylene oxide gas treatment therein. It is also a feature of the present invention to provide a printed informative device for ethylene oxide sterilization, which is cost effective, relatively simple to use, resists contaminating the goods being sterilized, and is environmentally friendly.
- the present invention provides water-based chemical indicator inks for ethylene oxide sterilization processes.
- the water-based chemical indicator ink contains at least one pH indicator dye.
- the pH indicator dye will undergo a visual, distinct and irreversible color change when exposed to ethylene oxide vapor in the presence of low-temperature steam. Accordingly, the water-based chemical indicator ink composition of the present invention can be applied to a substrate to form an ethylene oxide sterilization process indicator that is effective in signaling whether an article has been subjected to ethylene oxide sterilization processing.
- the water-based chemical indicator ink of the present invention merely shows that an article has undergone ethylene oxide sterilization processing. It does not indicate whether any microbial contaminants were effectively destroyed. Consequently, it is important for the operator of the ethylene oxide sterilization process to follow correct sterilization protocols.
- the efficacy of sterilization by ethylene oxide depends upon a number of factors, the most important of which are the concentration of the ethylene oxide in the sterilization vessel or chamber, the moisture present, the time of contact with the ethylene oxide, and the temperature of the treatment. Since one of the principal advantages of ethylene oxide sterilization is that it is effective at relatively low temperature, most sterilizers are operated at ambient temperature up to about 145°F (which falls within the definition of "low-temperature” as used herein). Humidity in the range from 40 to 60% relative humidity (which falls within the definition of "steam” as used herein) has been found to be most effective, and in practice this range can be maintained. The effects of time and concentration are inter-related and generally expressed as the lower the concentration, the longer time of exposure required to effect sterilization.
- telltales of the present invention measure the integrated effect of time of exposure, and the concentration of the ethylene oxide, in the presence of water vapor (i.e., "steam").
- the telltales depend upon the chemical reaction of ethylene oxide on magnesium chloride, crystallized with water, MgCl 2 .6H 2 O by which magnesium hydroxide and epichlorohydrin are produced.
- compositions are in the form of a dried printing ink, which is applied by the process of printing, particularly by flexographic printing of squares or insignia on a substrate.
- the freshly applied squares or insignia are allowed to dry, after which the printed indicators are used as telltales to indicate that moist ethylene oxide has been present in sufficient concentration for a long enough time to effectively sterilize the goods or articles contained in the sterilizing vessel or chamber.
- the indicator ink consists of a thickened liquid ink base, powdered magnesium chloride with water of crystallization (Mg Cl 2 ⁇ 6H 2 O), and a pH indicator dye.
- the chemical indicator ink of the instant invention which dries rapidly by evaporation, is water-based.
- the water-based chemical indicator ink consists generally of:
- the pH indicator dye can be Bromocresol green (cas. #76-60-8) or 3',3", 5',5"-tetrabromo-m-cresol sulfonephthalein.
- the chemical structure for this pH indicator dye is:
- the pH indicator dye can be Bromophenol blue (cas. #115-39-9) or 3',3", 5',5"-tetrabromophenol-sulfonephthalein.
- the chemical structure for this pH indicator dye is:
- the pH indicator dye can be Ethyl orange sodium salt (cas. #62758-12-7) or [4-(4-diethylaminophenylazo)benzenesulfonic acid, sodium salt].
- the chemical structure for this pH indicator dye is:
- the pH indicator dye can be Methyl red sodium salt (cas. #845-10-3) or ⁇ 2-[4-(dimethylamino)phenylazo] benzoic acid ⁇ sodium salt.
- the chemical structure for this pH indicator dye is:
- pH indicator dyes when subjected to ethylene oxide, exhibit a distinct and irreversible color change. The color changes are visually very marked. Consequently, it is readily apparent when viewing the ethylene oxide sterilization process indicator of the present invention whether the materials associated therewith have been subjected to ethylene oxide sterilization processing.
- Individual pH indicator dyes, each exhibiting a distinct color change can be combined to form a single chemical indicator ink that exhibits its own distinct color change.
- the colors of the individual and combined pH indicator dyes of the present invention both before and after exposure to ethylene oxide (ETO) vapor are set forth in Table 1 below. pH Indicator Dye(s) Before and After Exposure to ETO Vapor No.
- the water-based chemical indicator ink of the present invention can be an aqueous ink solution, wherein the pH indicator dye is dissolved in water.
- the water-based chemical indicator ink can further include a powdered and crystallized hexahydrate metal salt that provides water so as to facilitate the sterilization reaction, and/or an acidic compound, i.e., citric acid, which acts as a color retarder ingredient.
- the water-based chemical indicator ink can include a thickening agent such as talc (hydrous silicates of magnesium or aluminum).
- a white pigment such as titanium dioxide can be added to the water-based chemical indicator ink as a brightener for the pH indicator dye.
- Polyvinyl alcohol, methyl cellulose, and/or other polymeric materials can also be added to assist in binding and stabilizing the water-based chemical indicator ink until use.
- the water-based chemical indicator ink can further include a foam suppressor such as an aliphatic polyol blend.
- a method for indicating that an article has undergone ethylene oxide sterilization processing comprises providing a water-based chemical indicator ink as described herein, applying the ink to an artide, subjecting the article to a concentration of ethylene oxide vapor in the presence of low-temperature steam, and observing the ink for a color change that is visually indicative of whether the concentration of ethylene oxide vapor has been applied for a time sufficient to sterilize the article.
- the method can further comprise measuring the integrated effect of subjecting the article to the concentration of ethylene oxide vapor in the presence of low-temperature steam for the time sufficient to sterilize the article.
- the method can comprise applying the ink to a substrate to form an ethylene oxide sterilization process indicator prior to applying it to the article, or printing the ink on the substrate in the shape of squares or insignia.
- the method can comprise securing the ethylene oxide sterilization process indicator to a package containing an article and subjecting the package to ethylene oxide sterilization.
Abstract
Description
pH Indicator Dye(s) Before and After Exposure to ETO Vapor | |||
No. | pH Indicator Dye(s) | Color Before Exposure to ETO | Color After Exposure to ETO |
1 | Bromocresol green + Methyl red | Brick red | Blue |
2 | Bromophenol blue + Ethyl orange | Orange | Blue |
3 | Ethyl orange | Pink | Orange |
4 | Bromophenol blue | Yellow | Blue |
5 | Bromophenol blue + Methyl red | Brick red | Purple |
6 | Bromocresol green | Orange | Green |
Ingredients for Chemical Indicator Inks | |
Ingredient | Amount (g) |
Water | 39.02 |
15% Polyvinyl alcohol | 39.02 |
Thickeners | 7.57 |
Hexahydrate metal salt | 7.28 |
Citric acid | 3.989 |
pH indicators | 1.04 |
Methyl cellulose | 1.03 |
Foam suppressor | 0.033 |
pH Indicator Dye(s) Before and After Exposure to Different Sterilization Methods | |||||
No. | pH Indicator Dye(s) | Original Color | Dry Heat Sterilization | Steam Sterilization | Formaldehyde Sterilization |
1 | Bromocresol green + Methyl red | Brick red | No color change | No color change | No color change |
2 | Bromophenol orange + Ethyl orange | Orange | Dark green | Green | No color change |
3 | Ethyl orange | Pink | Brown | Dark pink | Brown |
4 | Bromophenol blue | Yellow green | Dark green | No color change | No color change |
5 | Bromophenol blue+ + Methyl red | Brick red | No color change | Pink red | No color change |
6 | Bromocresol green | Orange | Orange green | No color change | No color change |
Claims (38)
- A water-based chemical indicator ink for ethylene oxide sterilization processes containing at least one pH indicator dye selected from the group consisting of Bromocresol green, Bromophenol blue, Methyl red, Ethyl orange, and combinations thereof.
- The water-based chemical indicator ink of claim 1 wherein said at least one pH indicator dye undergoes an irreversible color change when exposed to ethylene oxide vapor in the presence of low-temperature steam.
- The water-based chemical indicator ink of claim 2 wherein said low-temperature steam has a temperature of less than about 145°F.
- The water-based chemical indicator ink of at least one of the preceding claims wherein said at least one pH indicator dye does not undergo a color change when exposed to formaldehyde gas, high-temperature steam, dry heat, or combinations thereof.
- The water-based chemical indicator ink of at least one of claims 1 to 3 wherein said at least one pH indicator dye undergoes a color change when exposed to formaldehyde gas, high-temperature steam, dry heat, or combinations thereof, that is different than is obtained when exposed to ethylene oxide vapor.
- The water-based chemical indicator ink of at least one of the preceding claims wherein said water-based chemical indicator ink is an aqueous ink solution.
- The water-based chemical indicator ink of claim 6 wherein said aqueous ink solution comprises said at least one pH indicator dye dissolved in water.
- The water-based chemical indicator ink of at least one of the preceding claims further containing a powdered and crystallized hexahydrate metal salt.
- The water-based chemical indicator ink of at least one of the preceding claims further containing an acidic compound, wherein said acidic compound retards a color change of said water-based chemical indicator ink.
- The water-based chemical indicator ink of claim 9 wherein said acidic compound is citric acid.
- The water-based chemical indicator ink of at least one of the preceding claims further containing at least one thickening agent.
- The water-based chemical indicator ink of claim 11 wherein said at least one thickening agent is selected from the group consisting of hydrous aluminum silicates, hydrous magnesium silicates, and combinations thereof.
- The water-based chemical indicator ink of at least one of the preceding claims further comprising a white pigment.
- The water-based chemical indicator ink of claim 13 wherein said white pigment is titanium dioxide.
- The water-based chemical indicator ink of at least one of the preceding claims further containing a binder.
- The water-based chemical indicator ink of claim 15 wherein said binder is a polymeric material.
- The water-based chemical indicator ink of claim 16 wherein said polymeric material is selected from the group consisting of polyvinyl alcohol, methyl cellulose, and combinations thereof.
- The water-based chemical indicator ink of at least one of the preceding claims further containing a foam suppressor.
- The water-based chemical indicator ink of claim 18 wherein said foam suppressor is an aliphatic polyol blend.
- A method for indicating that an article has undergone ethylene oxide sterilization processing comprising:providing a water-based chemical indicator ink containing at least one pH indicator dye selected from the group consisting of Bromocresol green, Bromophenol blue, Methyl red, Ethyl orange, and combinations thereof, wherein said at least one pH indicator dye undergoes an irreversible color change when exposed to ethylene oxide vapor in the presence of low-temperature steam;applying said water-based chemical indicator ink to an article;subjecting said article to a concentration of ethylene oxide vapor in the presence of low-temperature steam; andobserving said water-based chemical indicator ink for a color change that is visually indicative of whether said concentration of ethylene oxide vapor has been applied for a time sufficient to sterilize said article.
- The method of claim 20 further comprising measuring the integrated effect of subjecting said article to said concentration of ethylene oxide vapor in the presence of low-temperature steam for said time sufficient to sterilize said article.
- The method of claim 20 or 21 further comprising applying said water-based chemical indicator ink to a substrate to form an ethylene oxide sterilization process indicator prior to applying said water-based chemical indicator ink to said article.
- The method of claim 22 further comprising printing said water-based chemical indicator ink on said substrate in the shape of squares or insignia to form said ethylene oxide sterilization process indicator.
- The method of claim 22 or 23 further comprising securing said ethylene oxide sterilization process indicator to a package containing said article and subjecting said package to said concentration of ethylene oxide vapor in the presence of low-temperature steam.
- The method of at least one of claims 20 to 24 further comprising providing said water-based chemical indicator ink containing said at least one pH indicator dye wherein said at least one pH indicator dye does not undergo a color change when exposed to formaldehyde gas, high-temperature steam, dry heat, or combinations thereof.
- The method of at least one of claims 20 to 24 further comprising providing said water-based chemical Indicator ink containing said at least one pH indicator dye wherein said at least one pH indicator dye undergoes a color change when exposed to formaldehyde gas, high-temperature steam, dry heat, or combinations thereof, that is different than is obtained when exposed to ethylene oxide vapor.
- The method of at least one of claims 20 to 26 further comprising providing said water-based chemical indicator ink containing said at least one pH indicator dye and a powdered and crystallized hexahydrate metal salt.
- The method of at least one of claims 20 to 27 further comprising providing said water-based chemical indicator ink containing said at least one pH indicator dye and an acidic compound, wherein said acidic compound retards a color change of said water-based chemical indicator ink.
- The method of claim 28 wherein said acidic compound is citric acid.
- The method of at least one of claims 20 to 29 further comprising providing said water-based chemical indicator ink containing said at least one pH indicator dye and at least one thickening agent.
- The method of claim 30 wherein said at least one thickening agent is selected from the group consisting of hydrous aluminum silicates, hydrous magnesium silicates, and combinations thereof.
- The method of at least one of claims 20 to 31 further comprising providing said water-based chemical indicator ink containing said at least one pH indicator dye and a white pigment.
- The method of claim 32 wherein said white pigment is titanium dioxide.
- The method of at least one of claims 20 to 33 further comprising providing said water-based chemical indicator ink containing said at least one pH indicator dye and a binder.
- The method of claim 34 wherein said binder is a polymeric material.
- The method of claim 35 wherein said polymeric material is selected from the group consisting of polyvinyl alcohol, methyl cellulose, and combinations thereof.
- The method of at least one of claims 20 to 36 further comprising providing said water-based chemical indicator ink containing said at least one pH indicator dye and a foam suppressor.
- The method of claim 37 wherein said foam suppressor is an aliphatic polyol blend.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US178192 | 1998-10-23 | ||
US10/178,192 US6800124B2 (en) | 2002-06-24 | 2002-06-24 | Ethylene oxide sterilization process indicator inks |
Publications (2)
Publication Number | Publication Date |
---|---|
EP1374918A1 true EP1374918A1 (en) | 2004-01-02 |
EP1374918B1 EP1374918B1 (en) | 2008-08-06 |
Family
ID=29717881
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP03010105A Expired - Fee Related EP1374918B1 (en) | 2002-06-24 | 2003-05-05 | Ethylene oxide sterilization indicator inks |
Country Status (4)
Country | Link |
---|---|
US (2) | US6800124B2 (en) |
EP (1) | EP1374918B1 (en) |
CA (1) | CA2432748C (en) |
DE (1) | DE60322624D1 (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2005052572A1 (en) * | 2003-11-22 | 2005-06-09 | Agt Sciences Limited | Polymeric materials incorporating a ph indicator dye |
CN107617117A (en) * | 2017-10-09 | 2018-01-23 | 珠海天威飞马打印耗材有限公司 | A kind of oxirane sterilization chemical indicator composition and preparation method thereof, indicator tape |
Families Citing this family (30)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7244252B2 (en) * | 2003-11-25 | 2007-07-17 | Scimed Life Systems, Inc. | Medical device with visual indicator and related methods of use |
CN1860192A (en) * | 2004-08-19 | 2006-11-08 | 桑福德有限合伙人公司 | Decoder system |
KR20070085841A (en) | 2004-11-08 | 2007-08-27 | 프레쉬포인트 홀딩스 에스아 | Time-temperature indicating device |
US8497129B2 (en) * | 2006-03-17 | 2013-07-30 | Ethicon Endo-Surgery, Inc. | Reprocessing indicators for medical instruments |
US20070219563A1 (en) * | 2006-03-17 | 2007-09-20 | Voegele Aaron C | Reprocessing indicator ink for medical instruments |
US20080021392A1 (en) * | 2006-07-20 | 2008-01-24 | Lurvey Kent L | Medical fluid access site with antiseptic indicator |
US20080107564A1 (en) * | 2006-07-20 | 2008-05-08 | Shmuel Sternberg | Medical fluid access site with antiseptic indicator |
JP5118389B2 (en) * | 2007-05-26 | 2013-01-16 | 中村製作所株式会社 | Method for forming recess in workpiece |
US9125973B2 (en) | 2007-07-20 | 2015-09-08 | Baxter International Inc. | Antimicrobial housing and cover for a medical device |
USRE47452E1 (en) | 2007-07-20 | 2019-06-25 | Baxter International Inc. | Antimicrobial housing and cover for a medical device |
US20140154808A1 (en) | 2012-12-03 | 2014-06-05 | Gordhanbhai N. Patel | Monitoring system based on etching of metals |
CN102077060B (en) | 2008-06-04 | 2014-10-29 | G·帕特尔 | A monitoring system based on etching of metals |
EP2288879B1 (en) | 2008-06-04 | 2018-01-24 | G Patel | A monitoring system based on etching of metals |
US10219826B2 (en) | 2010-07-14 | 2019-03-05 | Seg-Way Orthopaedics, Inc. | Method and apparatus for endoscopic ligament release |
US8672960B2 (en) * | 2010-07-14 | 2014-03-18 | SEG-Way Orthopaedics, Inc | Method and apparatus for endoscopic ligament release |
US8628968B2 (en) | 2011-03-30 | 2014-01-14 | La-Co Industries, Inc. | Ethylene oxide sterilization indicator compositions |
EP2581422A1 (en) * | 2011-10-11 | 2013-04-17 | Sicpa Holding Sa | Ink coatings for security documents to prevent forgery by means of heat sensitive erasable ink |
US10004373B2 (en) * | 2012-09-17 | 2018-06-26 | Bissell Homecare, Inc. | Cleaning pad with visually discernible indicator, steam mop and method |
EP2900281B1 (en) | 2012-09-26 | 2019-09-18 | The Procter and Gamble Company | Liquid activated color change ink and methods of use |
US11542080B2 (en) | 2013-05-07 | 2023-01-03 | BBB Holding Company | Track and trace packaging and systems |
US20140334978A1 (en) * | 2013-05-10 | 2014-11-13 | Cdti | System and Apparatus for a Laboratory Scale Reactor |
US9289528B2 (en) * | 2013-06-26 | 2016-03-22 | Eastman Kodak Company | Methods for using indicator compositions |
US9291570B2 (en) * | 2013-06-26 | 2016-03-22 | Eastman Kodak Company | Reactive indicator compositions and articles containing same |
EP3073892B1 (en) | 2013-11-27 | 2020-02-12 | Trice Medical, Inc. | Surgical guide |
WO2015112679A1 (en) | 2014-01-27 | 2015-07-30 | Jp Laboratories, Inc | Indicating devices based on lateral diffusion of a mobile phase through a non-porous stationary phase |
CN105567020B (en) * | 2014-10-09 | 2018-06-12 | 3M创新有限公司 | Chemical indication composition, steam sterilizing indicant and preparation method thereof |
GB201603462D0 (en) * | 2016-02-29 | 2016-04-13 | Ge Healthcare Uk Ltd | Ethylene oxide treatment |
KR102324095B1 (en) * | 2019-05-22 | 2021-11-11 | 씨제이제일제당 주식회사 | pH response color change ink composition and pH response color change Label using the pH response color change ink composition and pH response color change Packaging material using the pH response color change ink composition |
JP2022529830A (en) * | 2019-05-22 | 2022-06-24 | シージェイ チェイルジェダン コーポレーション | A pH-sensitive discoloring ink composition, a pH-sensitive instruction label using the composition, and the packaging material. |
CN111410869A (en) * | 2020-04-23 | 2020-07-14 | 南京巨鲨显示科技有限公司 | Indicator and indicator label for low-temperature ethylene oxide sterilization |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB854142A (en) * | 1958-04-22 | 1960-11-16 | Boots Pure Drug Co Ltd | The control of bacteriological sterilisation |
US2998306A (en) * | 1960-04-15 | 1961-08-29 | Aseptic Thermo Indicator Compa | Telltale for ethylene oxide sterilization |
US3098751A (en) * | 1960-07-18 | 1963-07-23 | Aseptic Thermo Indicator Compa | Printing ink composition for ethylene oxide sterilization indicators |
US4145186A (en) * | 1976-10-04 | 1979-03-20 | H. W. Andersen Products Inc. | Sterilization detection device and method |
US4206844A (en) * | 1977-01-04 | 1980-06-10 | Toppan Printing Co., Ltd. | Package for a sterilized material |
JPS5710902B2 (en) * | 1974-06-11 | 1982-03-01 | ||
WO2001010471A1 (en) * | 1999-06-08 | 2001-02-15 | Patel Gordhanbhai N | Dosimeter for sterilization with ethylene oxide |
Family Cites Families (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2409215A (en) * | 1943-12-27 | 1946-10-15 | Interchem Corp | Printing ink |
US3227657A (en) * | 1962-09-20 | 1966-01-04 | Minerals & Chem Philipp Corp | Glycol coated attapulgite clay and compositions including the same |
DE2321755C2 (en) * | 1973-04-30 | 1982-07-01 | Henkel KGaA, 4000 Düsseldorf | Anti-foaming agents |
JPS602059B2 (en) * | 1976-11-22 | 1985-01-18 | 凸版印刷株式会社 | Sterilization packaging |
US4166044A (en) * | 1978-05-30 | 1979-08-28 | American Can Company | Binderless thermotropic jet ink |
US4362645A (en) * | 1978-09-28 | 1982-12-07 | Akzona, Inc. | Temperature indicating compositions of matter |
US5183742A (en) * | 1984-02-24 | 1993-02-02 | Dai Nippon Insatsu Kabushiki Kaisha | Test device for detecting glucose, protein urobilinogen, and/or occult blood in body fluids and/or determining the PH thereof |
CA2047202C (en) * | 1989-12-25 | 1999-03-30 | Hiroshi Ito | Sheet, seat, bag, article of daily use, ink and packaging material for animal |
US5254473A (en) * | 1990-03-16 | 1993-10-19 | Jp Laboratories | Solid state device for monitoring integral values of time and temperature of storage of perishables |
DE69303368T2 (en) * | 1992-05-28 | 1996-11-14 | Minnesota Mining & Mfg | INDICATOR TAPE AND METHOD |
US5591400A (en) * | 1994-10-31 | 1997-01-07 | Minnesota Mining And Manufacturing Company | Method for producing an ionic sensor |
US5990199A (en) * | 1995-04-19 | 1999-11-23 | North American Science Associates, Inc. | Indicator ink compositions |
WO1997035935A1 (en) * | 1996-03-27 | 1997-10-02 | Mitsubishi Pencil Kabushiki Kaisha | Water base ink having metallic luster for ball-point pen and aqueous pigment ink |
US6009339A (en) * | 1997-02-27 | 1999-12-28 | Terumo Cardiovascular Systems Corporation | Blood parameter measurement device |
US20030199095A1 (en) * | 2001-06-14 | 2003-10-23 | Kohei Yuyama | Ink composition for sensing carbon dioxside gas, carbon dioxside indicator using the same, package provided with the carbon dioxside indicator, and method for sensing pinhole using the same |
US20030211618A1 (en) * | 2001-05-07 | 2003-11-13 | Patel Gordhandhai Nathalal | Color changing steam sterilization indicator |
-
2002
- 2002-06-24 US US10/178,192 patent/US6800124B2/en not_active Expired - Fee Related
-
2003
- 2003-05-05 EP EP03010105A patent/EP1374918B1/en not_active Expired - Fee Related
- 2003-05-05 DE DE60322624T patent/DE60322624D1/en not_active Expired - Lifetime
- 2003-06-18 CA CA002432748A patent/CA2432748C/en not_active Expired - Fee Related
-
2004
- 2004-06-29 US US10/880,010 patent/US7141214B2/en not_active Expired - Fee Related
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB854142A (en) * | 1958-04-22 | 1960-11-16 | Boots Pure Drug Co Ltd | The control of bacteriological sterilisation |
US2998306A (en) * | 1960-04-15 | 1961-08-29 | Aseptic Thermo Indicator Compa | Telltale for ethylene oxide sterilization |
US3098751A (en) * | 1960-07-18 | 1963-07-23 | Aseptic Thermo Indicator Compa | Printing ink composition for ethylene oxide sterilization indicators |
JPS5710902B2 (en) * | 1974-06-11 | 1982-03-01 | ||
US4145186A (en) * | 1976-10-04 | 1979-03-20 | H. W. Andersen Products Inc. | Sterilization detection device and method |
US4206844A (en) * | 1977-01-04 | 1980-06-10 | Toppan Printing Co., Ltd. | Package for a sterilized material |
WO2001010471A1 (en) * | 1999-06-08 | 2001-02-15 | Patel Gordhanbhai N | Dosimeter for sterilization with ethylene oxide |
Non-Patent Citations (1)
Title |
---|
DATABASE WPI Section Ch Week 198212, Derwent World Patents Index; Class D22, AN 1982-23354E, XP002245210 * |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2005052572A1 (en) * | 2003-11-22 | 2005-06-09 | Agt Sciences Limited | Polymeric materials incorporating a ph indicator dye |
CN107617117A (en) * | 2017-10-09 | 2018-01-23 | 珠海天威飞马打印耗材有限公司 | A kind of oxirane sterilization chemical indicator composition and preparation method thereof, indicator tape |
Also Published As
Publication number | Publication date |
---|---|
US6800124B2 (en) | 2004-10-05 |
US20030235654A1 (en) | 2003-12-25 |
CA2432748A1 (en) | 2003-12-24 |
EP1374918B1 (en) | 2008-08-06 |
DE60322624D1 (en) | 2008-09-18 |
US7141214B2 (en) | 2006-11-28 |
CA2432748C (en) | 2008-12-30 |
US20040241862A1 (en) | 2004-12-02 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US6800124B2 (en) | Ethylene oxide sterilization process indicator inks | |
KR100691383B1 (en) | Chemical indicator, method for detecting the presence of hydrogen peroxide using the same and sterilizer system comprising the same | |
JP3290132B2 (en) | Composition for chemical indicator and sheet to which the composition is adhered | |
JP4109201B2 (en) | Hydrogen peroxide indicator, peracetic acid indicator, and method using the same | |
US6063631A (en) | Sterilization indicator | |
US3098751A (en) | Printing ink composition for ethylene oxide sterilization indicators | |
JPS6133659A (en) | Use of chlorine dioxide gas as chemical disconfecting agent | |
WO2004087222A1 (en) | Indicator for plasma sterilization and packaging material for sterilization | |
US4514361A (en) | Steam sterilization indicator | |
JP2002303618A (en) | Indicator for plasma sterilization and packaging material for sterilization | |
JP4111855B2 (en) | Plasma sterilization indicator and sterilization packaging material | |
EP1117294B1 (en) | Multi-part anti-microbial sterilization compositions and methods | |
US11484614B2 (en) | Water-based sterilization indicator composition | |
US20030113923A1 (en) | Steam-formaldehyde sterilization process indicator inks | |
JP5289590B2 (en) | Plasma sterilization indicator and sterilization packaging material | |
JP2002071570A (en) | Indicator for plasma sterilization and packaging material for sterilization | |
JP4936620B2 (en) | Plasma sterilization indicator and sterilization packaging material | |
US20220163496A1 (en) | Chemical Hydrogen Peroxide Indicator | |
JPH0372260A (en) | Indicator composition for detecting formalin sterilization | |
JPH03140159A (en) | Indicator composition for detecting formalin sterilization |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LI LU MC NL PT RO SE SI SK TR |
|
AX | Request for extension of the european patent |
Extension state: AL LT LV MK |
|
17P | Request for examination filed |
Effective date: 20040503 |
|
17Q | First examination report despatched |
Effective date: 20040614 |
|
AKX | Designation fees paid |
Designated state(s): DE FR GB IT |
|
GRAP | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOSNIGR1 |
|
GRAS | Grant fee paid |
Free format text: ORIGINAL CODE: EPIDOSNIGR3 |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): DE FR GB IT |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: FG4D |
|
REF | Corresponds to: |
Ref document number: 60322624 Country of ref document: DE Date of ref document: 20080918 Kind code of ref document: P |
|
PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
26N | No opposition filed |
Effective date: 20090507 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: ST Effective date: 20100129 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FR Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20090602 |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: 732E Free format text: REGISTERED BETWEEN 20130801 AND 20130807 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R082 Ref document number: 60322624 Country of ref document: DE Effective date: 20130911 Ref country code: DE Ref legal event code: R081 Ref document number: 60322624 Country of ref document: DE Owner name: LA-CO INDUSTRIES, INC., US Free format text: FORMER OWNER: ILLINOIS TOOL WORKS INC., GLENVIEW, US Effective date: 20130828 Ref country code: DE Ref legal event code: R081 Ref document number: 60322624 Country of ref document: DE Owner name: LA-CO INDUSTRIES, INC., ELK GROVE VILLAGE, US Free format text: FORMER OWNER: ILLINOIS TOOL WORKS INC., GLENVIEW, ILL., US Effective date: 20130828 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 20150528 Year of fee payment: 13 Ref country code: GB Payment date: 20150527 Year of fee payment: 13 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: IT Payment date: 20150527 Year of fee payment: 13 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R119 Ref document number: 60322624 Country of ref document: DE |
|
GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 20160505 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20160505 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20161201 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GB Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20160505 |